Conversion of hydrocarbons



Sept. 22, 1936. R RUTHRUFF 2,055,313

CONVERSION OF HYDROGARBONS Filed Aug. 31, 1934 IN V EN TOR. ROBERT F: RUTH/Pl}? BY m fl ATTORNEY Patented Se t. 22, 1936 2,055,313

UNITED STATES PATENT OFFICE 2.055.313 CONVERSION or nrnaocannons Robert Freehorn Ruthruff, Whiting, Ind., aasignor to Standard Oil Company (Ind.), Chicaso, 111., a corporation of Indiana Application August 31, 1934, Serial No. 142,205 14 Claims. '(oi. lac-1o) This invention relates in general to the converhot combustion gases and thereafter collected sion of hydrocarbon fluids and more especially in a body. The desired heating of the hydrocarto improvements in the art of thermally convertbon fluid to a conversion temperature may be acing hydrocarbon fluids wherein such a fluid is complished by passing it in heat exchange rela- 5 heated to the desired elevated temperature by tion with the body of molten material, without 5 passing it in heat exchange relation with a fluid either the hot combustion gases or the hydroheat transfer medium, such as molten material, carbon fluid coming into direct contact with each the fluid heat transfer medium being circulated other. It will, therefore, be evident that my infrom' and to a reaction chamber of an apparatus vention provides for the necessary heating and for carrying out the process by another medium conversion of the hydrocarbon fluid to produce 10 capable of exerting a gas lift effect thereon with the desired product, such as a motor fuel of the provision being made for the heating of the gasoline boiling range, without the necessity of molten material during circulation thereof, prefsubsequent separation of the eiliuent resulting erably, by directly contacting it with hot gaseous from the heat treatment of the hydrocarbon fluid or vaporous fluid. and the hot combustion gases directly contacted 15 As contemplated by my invention, a body of with the molten material for the purpose of heatfluid heat transfer medium, such as a molten ing it to the desired elevated temperature.. material, may be maintained at an elevated tem- In order to make my invention more clearly perature in a reaction chamber of a suitable apunderstood, I have shown in the accompanying o paratus. The molten material may be circulated drawing, means for carrying the same into pracfrom and to said body by introducing directly tical effect without limiting the improvements into a stream thereof, withdrawn from the body in their usefulapplications to the particular conof molten material, a medium capable of exertstructions which, for the purpose of explanation, ing a gas lift effect on the molten material to have been made the subject of illustration.

5 effect circulation thereof, such as hot combustion Figure 1 is an elevational view of an apparatus gases, these hot gases heating the molten material capable of carrying out my invention. to an elevated temperature during the circulation Figure 2 is an elevational view of another type thereof before the circulating molten material is of apparatus also capable of carrying out my collected in said body. My invention also coninvention.

templates effecting circulation of molten material Referring to Figure 1 wherein circulation and so from and to said body maintained in the reaction heating of the molten material may be simulchamber by introducing a hydrocarbon fluid, such taneously accomplished by introducing hot 'comas a liquidoil, under superatmospheric pressure bustion gases into a stream of molten material, into a stream thereof withdrawn from the body, there is shown an enlarged vessel I having a 5 the hydrocarbon fluid being preheated while exreaction chamber 2 at the lower portion thereerting a gas lift effect on the molten material. of. The reaction chamber 2 may be separated During the circulation of the molten material by from the upper portion of the vessel l by means the hydrocarbon fluid, the molten material is of a dome-plate 3. The vessel I may also be heated by direct contact with hot combustion provided with a conduit 6 within the vessel for 40 gases to elevate the temperature thereof prior returning molten material heated to an elevated 40 to its being collected inthe aforementioned body. temperature to a body thereof collected in the The hydrocarbon fluid after being preheated in reaction chamber 2. The conduit 4 may have a effecting circulation of molten material may trough arrangement 8 at the upper end therethereafter be passed in heat exchange relation of for directing reheated molten material, as

5 with the body of molten material collected in the will hereinafter be explained, returned to the reaction chamber and heated to the desired eleupper portion of the vessel; through the convated temperature. duit 4 into a trap 8 immersed in a body of My invention further contemplates withdrawmolten material I, collected in the reaction ing the hot combustion gases used to heat the chamber 2. 5o molten material from the apparatus independ- A conduit 8 extends from the lower portion so ently of the heated hydrocarbon. Thus circulaof the reaction chamber 2 to the upper part of tion of molten material is effected by a medium the vessel l. The molten material is circulated that exerts a gas lift effect thereon, the molten from the body thereof in the reaction chamber material being heated to an elevated temperature 2 to the upper portion of the vessel I through during circulation thereof by direct contact with the conduit 8, which may extend into the vessel 55 I I the. reaction chamber as -i the dome-plate [pipe IS. The molternmaterial is thus forced in as indicated at 9, the molten material thereafter dropping through part of the vessel into the trough from which it is directed to the trap 6 immersed in the body of molten material 1.

In order to force the molten material from the body 1 to the upper part of the vessel I and to heat it during its circulation from and to the body of molten material, there may be provided an inlet II for introducing hot products of combustion, produced in any suitable manner, such as by high pressure burners, directly into the molten material in the conduit 8. The hot comperature during the raising thereof. Thus molten material is circulated from the body 1 through the conduit 8 wherein it is heated to an elevated temperature and returned to the body 1 by means of the trough 5 and the con molten material. The hot combustion gases used to simultaneously circulate and heat the molten material may be withdrawn through an outlet l2 at the upper portion of the vessel I.

A hydrocarbon fluid, such as a clean gas oil, to be heated and converted into low boiling products, such as gasoline, may be introduced into the body of molten material by means of an inlet pipe I 3 connected to a spray nozzle I4 immersed in the body of molten material. The hydrocarbon fluid to be converted is preferably preheated in any suitable manner and thereafter passed in heat exchange relation with the body of molten material in a relatively short period of time to thereby rapidly raise it to the desired conversion temperature. The thus heated hydrocarbon may be withdrawn after passing in heat exchange relation with the molten material apparatus well known in highly heated hydrocarbon.

In accordance with my invention the hydrocarbon fluid is preferably introduced into the body of molten material at a high superatmospheric pressure, this pressure exerting itself on the column of molten material maintained in well as the conduit 8 connected thereto-due to the sealing effect of 3 and a suitable valve in the the conduit 8 to a higher level than that maintainedjin the reaction chamber 2.

the hydrocarbon fluid may be passed in indirect :heat exchange with the body of molten materailby using a suitable heating coil immersed therein, maintained directly on the body of terial in any suitable manner.

In lieu of withdrawing the combustion gases utilized as a gas lift medium as well as a heating medium for the molten materiaithrougb molten mathe conduit l2, the combustion gases may be passed through an opening With such an arrangement IS in the trough 5. the molten material receives any additional heat remaining in the hot gases through the conduit 4. The combustion gases after additionally heating the molten material in the conduit 4 may be withdrawn the outlet l 2"being closed by any suitable valve means.

If desired,

the desired elevated pressure being through the line As indicated in Figure 1, the height of molten same as the height of molten material in the conduit 8, to obtain the desired hydrostatic balance.

If a longer time of contact is desired between the combustion gases and the molten material in order to heat the latter to the desired elevated temperature during the circulation thereof, the draft gauge principle may be employed. This principle involves the lengthening of the conduit 8 from the point of the introduction of the hot combustion gases by inclining it from the horizontal to obtain a longer time of contact.

In Figure 2 I have shown an apparatus wherein the molten material maybe circulated from and to the body tion chamber by introducing a hydrocarbon fluid thereinto, the hydrocarbon fluid exerting a gas lift effect thereon and at the same time being preheated to the desired elevated temperature. In this modification, the molten material during circulation from and to the body may be heated by directly contacting it with hot combustion gases. In this figure, there is shown a vessel 2| having a reaction chamber 22 at the lower portion thereof. The reaction chamber 22 is separated from the upper portion of the vessel 2| by means of a trough 24, suitably secured to the sides of the vessel and having a conduit 23 associated therewith. The trough 24 and conduit 23 direct the descending molten material into a trap 25 immersed in a body of molten material 26. A conduit 21 may be connected to the reaction chamber 22 for conveying molten material from the body thereof maintained in the reaction chamber to the upper portion of the vessel. The molten material upon entering the upper portion of the vessel falls into a trap device indicated generally by the numeral 28. The trap device 28 may comprise a trough arrangement 29 secured to the sides of the vessel for directing the molten material through a passage 30 formed by a suitable conduit to the end 3| from which it is forced due to the accumulation of molten material through the space surrounding the passage 30 to an overflow point 32, from which it falls, through the trough 24 to the body of molten material maintained in the reaction chamber 22. v

In order to effect circulation of the molten material from the body 26 to the upper portion of the vessel, a stream of hydrocarbon fluid, such as a clean gas 'oil,'may be introduced through a pipe 33 and forced by means of a pump 34 directly into the molten material maintained in the conduit 21. The hydrocarbon fluid is vaporized upon contacting the molten material the thus vaporized hydrocarbon fluid exerting a'gas lift effect upon molten material in the conduit 21 and thereby raising it to the upper part of the vessel through the conduit 21 from which it falls into the trap 28 and overflows therefrom at the point 32; When a gas oil is introduced 33 or a heavier oil, any unvaporized products collecting in the passage 30 may be withdrawn through a suitable line 35. The

the distance between nd and up to a few seconds downwardly flowing molten material, the hot combustion gases after giving up their heat 'to the molten material leaving the vessel through a conduit 31.

vaporized constituents of the oil introduced through the line 33 rise to the upper portion of the vessel 2| and may be conducted through a line 38 into the body of molten material for further cracking or conversion by means of a suitable spray nozzle 39 immersed therein.

It will thus be evident from the foregoing that circulation of molten material from and to the body maintained in the reaction chamber 22 is effected by the hydrocarbon fluid introduced into the conduit 21, this hydrocarbon fluid being vaporized and exerting a gas lift effect on the molten material. The molten material after being utilized as a heat transfer medium to preheat the hydrocarbon fluid may be heated by direct contact with the combustion gases.

The height of molten material collected in the conduit 23 prior to being directed to the body 26 is as great as the height of molten material in the conduit 21 thus forcing the molten material through the conduit 21 to a point above where the medium for exerting a gas lift effect is introduced. If desired the molten material may be maintained at a greater height inthe conduit 23. As shown in the drawing, the distance between the bottom of the trap 28 and the overflow point 32 is approximately equal to the point of introduction of the hydrocarbon vapors into the body of molten material through the spray 39 and the height of the molten material in the conduit 23. The distance first mentioned should always be as great or greater than the second. mentioned distancev to insure that vaporized oil does not pass through the trap 28 and out over the overflow point 32.

In both of the modifications herein shown for carrying out my invention, the hotv combustion gases utilized to heat the molten material to an elevated temperature are withdrawn from the apparatus independently of the hydrocarbon fluid heated to the desired conversion temperature. Thus when practicing my invention there is no necessity for providing equipment to separate out the waste combustion gases from the more desirable products resulting from the conversion operation, the desirable products being treated in any suitable manner fuel, such as gasoline.

In operating my invention in accordance with the showing of Figure 1, the body of molten material 1 may be maintained at a temperature of about 1000-1200 F. and a hydrocarbon fluid,

such as a clean gas oil preheated to a temperature of about 800 F. and while under a pressure of about 200 to 300 pounds per square inch or as high as a thousand pounds, may be passed through the body of molten material in a relatively short period of time, preferably in the order of one secand raised to ahigh temperature of about 1000 F. The molten material being circulated from and to the body thereof may be contacted by hot combustion gases introduced through the conduit H at a temperature of about 2000-3000 F. while undena pressure of from to 50 pounds per square inch or as much higher as desired. These hot gases exert a gas lift effect on the molten material and simultaneously heat it to the aforementioned temperature prior to its return to the body in the reaction chamber 2.

- bon fluid, such as a clean gas for the recovery of motor my invention in an appain Figure 2, the body of When carrying out ratus of the type shown molten material 26 may be maintained at a temperature of from 1000-1200 F. and a hydrocaroil, introduced into the molten material in the conduit 21 under a pressure up to a'thousand pounds to thus be preheated and, if desired, subjected to thermal conversion by the molten material or cracking and also exert a gas lift effect thereon to cause circulation from the body 26 through the conduit 21 back to the body 26. The molten material before entering the body 26 may be heated to an elevated temperature by introducing combustion gases at a temperature of from 2000-3000 F. into direct contact therewith through the conduit 36, these combustion gases after passing-in direct contact with the descending molten material leaving the vessel through the conduit 31.

The hydrocarbon fluid in raising the molten material through the conduit 21 into the u p r part of the vessel 2| is preheated to a temperature upwards of 800 F. which results in vaporization of this oil. The vaporized constituents are conducted through the line 38 into the body of molten material through the nozzle 39 .wherein they are directly contacted with the molten material and therein rapidly raised to a temperai any suitable alloy of various metals, or fused salts, such as sodium hydroxide or a mixture of fused salts such as sodium and aluminum chloride may be employed. The expression molten material used throughout the specification and claims is intended to include any suitable metal alloy of various m tals, salts or mixture of various salts.

While my invention has been specifically described in connection with the cracking of a relatively clean gas oil, it is to be clearly understood that other hydrocarbon fluids may also be thermally converted in accordance therewith. For instance, my invention is also applicable to the thermal conversion of normally gaseous saturated hydrocarbons, for the production of gaseous oleflns or normally liquid products, and when practicing it in such a manner, temperatures above 1300 and as high as 1600 F. and higher and lower pressures may be employed.

While I have shown and described the preferred embodiment of my invention, and specific examples for each, I wish it to be understood that I 'do not confine myself to the precise details of construction herein set forth, by way of illustration, as it is apparent that many changes and variations may be made therein, by those skilled in the art, without departing from the spirit of the invention, or exceeding the scope of the appended claims.

1. In the art of thermally converting hydrocarbons, the method that comprises maintaining a body of molten material at elevated temperature in a conversion zone, circulating molten material from and to said conversion zone by introducing thereinto a fluid capable of exerting a gas lift eifect on the molten material, heating said molten material during the circulation and before collection thereof in said body by direct contact with hot gases introduced into intimate contact therewith to raise it to an elevated temperature, passing a hydrocarbon fluid in heat exchange relation with the body of molten material in the conversion zone to thereby raise it to the desired conversion temperature, withdrawing the thus heated hydrocarbon fluid from said conversion zone and withdrawing the hot gases after passing in direct contact with said molten material independently of said heated hydrocarbon fluid.

2. In the art of thermally converting hydrocarbons the method that comprises maintaining a body of molten material at elevated temperature in a conversion material from and to said conversion zone by introducing thereinto a fluid capable of exerting a gas lift eiTect on the molten material, heating said molten material during the circulation and before collection thereof in said body by direct contact with hot gases introduced into intimate contact therewith to raise it to an elevated temperature, passing a hydrocarbon fluid in direct contact with the body of molten material in the conversion zone to thereby raise it to the desired conversion temperature, withdrawing the thus heated hydrocarbon fluid from said conversion zone and withdrawing the hot gases after passing in direct contact with said molten material independently of said heated hydrocarbon fluid.

3. In the art of thermally converting hydrocarbons, the method that comprises maintaining a body of molten material at elevated temperature in a conversion zone, circulating molten material from and to said conversion zone by introducing thereinto a fluid capable of exerting a gas lift effect on the molten material, heating said molten material during the circulation and before collection thereof in said body by direct contact with hot gases introduced into intimate contact therewith to raise it to an elevated temperature, passing a hydrocarbon fluid in heat exchange relation with the body of molten material in the conversion zone to thereby raise it to the desired conversion temperature, independently withdrawing the thus heated hydrocarbon fluid from said conversion zone and the hot gases after giving up heat without either the heated hydrocarbon fluid or the hot gases coming into direct contact with each other.

4. In the art of thermally converting hydrocarbons, the method that comprises maintaining a body of molten material at elevated temperature in a conversion zone, introducing hot combustion gases at a superatmospheric pressure directly into intimate contact with molten material separate from said conversion zone to thereby heat molten material to-an elevated temperature prior to collection thereof .in said body and simultaneously efiect circulation thereof from and tosaid conversion zone by the gas lift efiect of the combustion gases, passing a hydrocarbon fluid in heat exchange relation with the body of molten material in the conversion zone to thereby raise it to the desired conversion temperature, withdrawing the thus heated hydrocarbon fluid from said conversion zone and withdrawing the hot combustion gases after heating said molten material independently of said heated hydrocarbon fluid and without coming into direct contact therewith.

5. In the art of thermally converting hydromolten material from zone, circulating molten' body of molten material carbons, the method that comprises maintaining a body of molten material at elevated temperature in a conversion zone, passing a stream of said conversion zone to another zone separate from said conversion zone, introducing hot combustion gases at a superatmospheric pressure directly into intimate con tact' with molten material in said last mentioned zone to thereby heat said molten material to an elevated temperature prior to collection thereof in said body and simultaneously efiect circulation thereof back to said conversion zone by the gas lift eifect of the combustion gases, passing a hydrocarbon fluid in heat exchange relation with the molten material in the conversion zone to thereby raise it to the desired conversion temperature, Withdrawing the thus heated hydrocarbon fluid from said conversion zone and withdrawing the hot combustion gases after heating said molten material independently of said heated hydrocarbon fluid and without coming into direct contact therewith.

6. In the art of thermally converting hydrocarbons, the method that comprises maintaining a body of molten material at elevated temperature in a conversion zone, introducing hot combustion gases at a superatmospheric pressure directly into intimate contact with molten material separate from said conversion zone to thereby heat molten material to an elevated temperature prior to collection thereof in said body and simultaneously effect circulation thereof from and to said conversion zone by the gas lift effect of the combustion gases, passing a hydrocarbon fluid in direct contact with the molten material in the conversion zone to thereby raise it to the desired conversion temperature, withdrawing the thus heated hydrocarbon fluid from said conversion zone and withdrawing the hot combustion gases after heating said molten material independently of said heated hydrocarbon fluid and without coming into direct contact therewith.

'7. In the art of thermally converting hydrocarbons, the method that comprises maintaining a at elevated temperature introducing a hydrocarbon hydrocarbon fluid, passing hot combustion gases directly into intimate contact with said circulating molten material to heat it to an elevated temperature prior to its being returned to the body thereof maintained in the conversion zone, conducting said hydrocarbon fluid after being heated heated hydrocarbon pressure into molten material in said last mentioned zone to thereby heat said hydrocarbon fluid to an elevated temperature and effect circulation of molten material from and to said conversion zone through said separate zone by the gas lift effect'of the hydrocarbon fluid, passing hot combustion gases directly into intimate contact with said circulating molten material to heat it to an elevated temperature prior to its being returned to the body thereof maintained in the conversion zone, conducting said hydrocarbon fluid after being heated to an elevated temperature in heat exchange relation with the molten material in the conversion zone to thereby raise it to the desiredconversiontemperature, withdrawing the thus heated hydrocarbon fluid from said conversion zone and withdrawing the hot gases after passing in contact with said molten material independently of said heated hydrocarbon fluid and without coming into direct contact therewith.

9. In an apparatus for the heat treatment of hydrocarbon fluids, an enlarged vessel, a reaction chamber at one end thereof, a body of molten material within said reaction chamber, a conduit exterior of said vessel and connected at one end to the reaction chamber and at the other end to said vessel beyond the reaction chamber, means directly connected to said conduit for introducing hot gases directly into said conduit to raise molten material fromsaid reaction chamber in said conduit back to said vessel by the gas lift effect produced thereby and heat the molten material to an elevated temperature prior to its return to said body thereof, means for introducing a hydrocarbon fluid to be heated into heat exchange relation with said body of molten material in the reaction chamber and means for withdrawing the thus fluid from said reaction chamber.

10. In an apparatus for the heat treatment of hydrocarbon fluids, an enlarged vessel, a reaction chamber at one end thereof, a body of molten material within said reaction chamber, a conduit exterior of said vessel and connected at one end to the reaction chamber and at the other end to said vessel beyond the reaction chamber, means directly connectedto said conduit for introducing hot gases directly into said conduit to raise molten material from said reaction chamber in said conduit back to said vessel by the gas lift effect produced thereby and heat the molten material to an elevated temperature prior to its return to said body thereof, means for preventing the hot gases from coming in contact with said body of molten material in said reaction chamber, means for introducing a hydrocarbon fluid to be heated into heat exchange relation with said body of molten material in the reaction chamber, means for withdrawing the thus heated hydrocarbon fluid from said reaction chamber, and means for withdrawing the combustion gases independently of said heated hydrocarbon fluid.

11. In an apparatus for the heat treatment of hydrocarbon fluids, an enlarged vessel, a reaction chamber at one end thereof, a body of molten material within said reaction chamber, a conduit exterior of said vesseland connected at one end to the reaction chamber and at the other end to said vessel beyond the reaction chamber, means directly connected to said conduit for introducing hydrocarbon fluid directly into said conduit under superatmospheric pressure to contact molten material therein thereby elevating the temperature of said hydrocarbon fluid and raising molten material from said reaction chamber in said conduit back to said vessel by the gas lift effect produced thereby, means for introducing hot combustion gases into direct contact with said circulating molten material to heat it to an elevated temperature prior to its return to said body in the reaction chamber, means for conducting said hydrocarbon fluid at elevated temperature to said body of molten material and passing it in heat exchange relation therewith to thereby raise the temperature of the hydrocarbon fluid and meansfor withdrawing the thus heated hydrocarbon fluid from said reaction chamber.

- 12. In an apparatus for the'heat treatment of hydrocarbon fluids, an enlarged vessel, a reaction chamber at one end thereof, a body of molten material within said reaction chamber, a conduit exterior of said vessel and connected at one end to the reaction chamber and at the other end to saidvessel beyond the reaction chamber, means directly connected to said conduit for introducing hydrocarbon fluid directly into said conduit under superatmospheric pressure to contact molten material therein thereby elevating the temperature of said hydrocarbon fluid and raising molten material from said reaction chamber in said conduit back to said vessel by the gas lift effect produced thereby, means for introducing hot combustion gases directly into contact with said circulating molten material to heat it to an elevated temperature prior to its return to said body in the reaction chamber, means for preventing the combustion gases from coming in contact with said body of molten material in said reaction withdrawing the thus heated hydrocarbon fluid from said reaction chamber and means for with-' drawing the combustion gases independently oi. said heated hydrocarbon fluid. 5

13. In apparatus for the heat treatment of hydrocarbon fluids, a vertical chamber, a body of molten material in the lower portion thereof to constitute a reaction zone, a conduit exterior of said chamber and connected at action zone of said chamber and at the other end to the upper end of said chamber beyond said reaction zone, means directly connected to said conduit for introducing directly thereinto a fluid adapted to raise molten material from said reaction zone in said conduit by the gas lift effect produced thereby and thus deliver molten material into the upper portion of said chamber and establish a cyclic movement of molten material between said conduit and said chamber, means for introducing a hydrocarbon fluid for heat treatment into heat exchange relation with thebody of molten material in said reaction zone, means vided with partitioning means to separate said chamber into an upper section and a lower section, a body of molten material in the lower section to constitute a reaction zone, a restricted passageway formed in said partitioning means adapted to constitute means for the delivery of molten material from the upper section into the lower section of said chamber and formed to protherewith to thereby raise the 3 one end to the revide a seal preventing the passage of fluids from the lower section to the upper section, a conduit exterior of said chamber and connected at one end to th'e'reaction zone in the lower section of said chamber and at the other end to the upper section of said chamber, means directly connected to said conduit for introducing directly thereinto a fluid adapted to raise molten material from the lower section of the reaction chamber in said conduit by the gas lift eflect produced thereby and thus deliver molten material into the upper section of the chamber and establish a cyclic movement of molten material between said conduit and said chamber, means for introducing a hydrocarbon fluid for heat treatment into heat exchange relation with the body of molten mate rial in the reaction zone in the lower section of the chamber, means for withdrawing the thus heated hydrocarbon fluid from the lower section of the chamber, and means for introducing hot gases into contact with the molten material during a portion of the lower section of the reaction chamber.

ROBERT FREEBORN RUTHRUFF.

its cyclic movement outside of 10 

